EP2212031B1 - Procédé de production d'un fini à effet métallique poli sur un véhicule - Google Patents

Procédé de production d'un fini à effet métallique poli sur un véhicule Download PDF

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Publication number
EP2212031B1
EP2212031B1 EP08858291.1A EP08858291A EP2212031B1 EP 2212031 B1 EP2212031 B1 EP 2212031B1 EP 08858291 A EP08858291 A EP 08858291A EP 2212031 B1 EP2212031 B1 EP 2212031B1
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EP
European Patent Office
Prior art keywords
waterborne
basecoat
composition
waterborne basecoat
basecoat composition
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EP08858291.1A
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German (de)
English (en)
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EP2212031A2 (fr
Inventor
Wilfried Dutt
James G. King
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Coatings Foreign IP Co LLC
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Coatings Foreign IP Co LLC
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Publication of EP2212031A2 publication Critical patent/EP2212031A2/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • B05D5/068—Metallic effect achieved by multilayers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/574—Three layers or more the last layer being a clear coat at least some layers being let to dry at least partially before applying the next layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together

Definitions

  • the present invention relates to coating methods. More particularly, the invention relates to an improved method for producing highly reflective coatings, on an automobile or truck body or part thereof.
  • a typical automobile steel panel or substrate has, for example, several layers of coatings.
  • the substrate is typically first coated with an inorganic rust proofing zinc or iron phosphate layer over which is provided a corrosion resistant primer, which can be an electrocoated primer or a repair primer.
  • a typical electrocoated primer which is mainly used in original equipment manufacturing (OEM) applications, comprises epoxy polyester and various epoxy resins.
  • OEM original equipment manufacturing
  • a primer surfacer and/or sealer can be applied over the electrodeposited primer to provide a smooth surface for better appearance and to which the overlying layer or layers of basecoat will readily adhere.
  • the cured primer layer can be sanded to remove any defects present such as, for example, dust particles in or on the primer or other imperfections.
  • pigmented basecoat layers and/or "effect" basecoat layers are applied over the primer layer.
  • Multiple basecoat layers can be applied depending upon the color and effect(s) that are desired in the finished product.
  • the multiple layers can either be the same as each other or different from each other.
  • rapid drying When rapid drying is required in a painting process, it is conventional to use equipment such as blowers and/or heaters to remove at least 50% of a dispersant solvent from a first coating layer prior to application of a second coating layer having a different composition during the period of time allotted for painting a vehicle substrate.
  • equipment such as blowers and/or heaters to remove at least 50% of a dispersant solvent from a first coating layer prior to application of a second coating layer having a different composition during the period of time allotted for painting a vehicle substrate.
  • Simple evaporation under ambient conditions or reliance upon movement of air around a substrate as the substrate is moved along a paint process line is not adequate for rapid drying processes and, therefore, are not used conventionally where rapid drying processes -- such as forced drying -- are required.
  • Metal flake pigments come in a variety of shapes and sizes. Conventional effect finishes typically are relatively thick metal flake pigments that impart a sparkle to the finished substrate. Several pigment manufacturers produce thin metal flake pigments. It is possible to produce coatings using these thin metal flake pigments that have a polished or anodized metal look without the metallic sparkle imparted by thick metal flake pigments. However, thin metal flake pigments are difficult to use in a coating composition as they allow underlying surface defects, such as sanding scratches, to be readily visible in the finished substrate.
  • the thin metal flake pigments are thin and flexible enough so as to conform to the topography of the underlying substrate. In this manner, during the solvent evaporation process, if thin metal flake pigments encounter a surface defect such as a sanding scratch, the flakes align and follow the topography of the defect. When the coating is dried and cured, the defect can be readily visible to the naked eye. In contrast, traditional metal flake pigments are thick enough so that they are able to lie flat on a substrate surface and bridge any sanding scratch defect without deforming. Such small scratches do not significantly affect a basecoating composition containing traditional metal flake pigments. Such traditional metal flake pigments typically have an average thickness of about 300 to about 500 nanometers whereas the thin metal flake pigments have an average thickness of only about 10 to 100 nanometers.
  • VMF vacuum metallized flake
  • US 2004/02882 describes a process and materials for coating motor vehicles with flake containing tricoat color finishes in a wet-on-wet-on-wet system on a continuously moving paint application line It would be desirable to eliminate multiple spray passes and baking steps in a process for manufacturing a vehicle having a polished metal appearance.
  • the present invention is directed to the process according to claim 1.
  • the coating process for applying a multi-layer coating is carried out using painting equipment that consists of two waterborne basecoat spray stations and one clearcoat spray station.
  • the method of this invention can be operated in a single pass continuous in-line paint application process or in stationary batch process such as a modular process.
  • the present invention eliminates the need for multiple bakes, while at the same time provides a waterborne finish that is of automotive quality and appearance, substantially free of sand scratch marks, and has smooth polished metal appearance with desired brightness, flop and with a minimum of sparkle metallic effect.
  • FIG. 1 is a general flow diagram of one embodiment of the present invention to achieve a polished metal appearance.
  • the present invention is a process for applying a multilayer coating on a vehicle, wherein the coating provides a polished metal appearance to the coated vehicle.
  • the present invention provides such an appearance on a vehicle that is substantially free from sand scratch marks, and thereby substantially reducing or eliminating altogether the manifestation of scratches and/or sanding defects that can be discerned at the outermost coating layer.
  • substantially free of sand scratch marks it is meant that a substrate coated according to the present invention is high enough in quality that no additional repair or retouching of the painted surface needs to be performed.
  • the cured coating might have defects that need to be repaired, such as, for example, dust particles on or under the paint.
  • small sanding scratches that may be present in the primer layer are generally not visible after application of the coating composition according to the present methods.
  • polishing metal or “anodized metal” appearance can be used interchangeably and as used herein describe a coating having a high flop value and a low texture and sparkle value. These values can be measured using a BYK-MAC 6-angle instrument, available from Byk-Gardner USA, Columbia, Maryland. This instrument can measure reflected light at several angles to determine the flop value, a “sparkle” value and a texture value that is termed “graininess” or "coarseness” value.
  • the film-forming portion of the coating composition of this invention is referred to as the "binder” or "binder solids".
  • the binder generally includes all the film-forming components that contribute to the solid organic portion of the cured composition. Generally, catalysts, pigments, and non-polymeric chemical additives such as stabilizers are not considered part of the binder solids.
  • binder or “binder solids” refers to the curable film-forming materials, the crosslinking agent and all other optional film-forming components, as are further described hereinbelow.
  • a polished metal or anodized metal looking finish of automotive quality that is substantially free of sand scratch marks is produced in a single pass using conventional basecoat/clearcoat continuous paint application lines typical of conventional automobile painting.
  • a substrate Prior to treatment, according to the process of this invention, a substrate optionally can be primed or otherwise treated as may be conventional in the art.
  • the vehicle body is pre-primed with a primer surfacer (also known as a primer sealer) layer and then sanded as needed to remove any defects, to a smooth finish as is conventional in the art.
  • a primer surfacer also known as a primer sealer
  • a first waterborne basecoat is applied to the surface of the automotive substrate (10).
  • the first waterborne basecoat is substantially free from thin metal flake pigments.
  • the phrase "substantially free from” as used herein means that the first waterborne basecoat comprises less than 1 percent by weight of a thin metal flake, such that the effects of the thin metal flake are not discernable on coated surface.
  • the first waterborne basecoat functions (a) to form a layer that fills any sanding scratch defects and (b) to provide a smooth surface on which the second waterborne basecoat can be applied.
  • the first waterborne basecoat composition can be applied to the surface of the substrate in this step by any suitable coating process well known to those skilled in the art.
  • a preferred method to apply the first waterborne basecoat is using electrostatic or pneumatic spray equipment.
  • the method and apparatus for applying the waterborne basecoat composition to the substrate is determined in part by the configuration and type of substrate material.
  • the process of the present invention includes a second step 24 of applying the second layer of waterborne basecoat composition containing thin metal flake pigment over the layer of first waterborne basecoat composition.
  • the second waterborne basecoat composition can be applied to the surface of the substrate in this step by any suitable coating process known to those skilled in the art.
  • a preferred method of applying the second waterborne basecoat is using pneumatic or electrostatic spray equipment.
  • the second waterborne basecoat composition can be applied within about 10 to 300 seconds of the first waterborne basecoat application, preferably within about 1 to 4 minutes of application.
  • basecoat application zone 22 and basecoat application zone 24 can be individual spray booths or can be the same spray booth. In some existing OEM automotive basecoat painting lines, basecoat zones 22 and 24 are the same spray booth. Two separate sets of spray guns are used to apply the layers of the first and second waterborne basecoat compositions and in many cases, the application of the second waterborne basecoat (onto the first waterborne basecoat) begins prior to the complete application of the first waterborne basecoat to the entire substrate.
  • the second waterborne basecoat is applied over the first waterborne basecoat before the first waterborne basecoat is dry.
  • the second waterborne basecoat containing the thin metal flake pigment can be applied to the first waterborne basecoat in such a manner that at least 50 percent, preferably at least 65 percent and more preferably, at least 80 percent by weight of the carrier liquid of the first waterborne basecoat is still present when the second waterborne basecoat is applied.
  • a forced drying step or intermediate flash step before the application of the second waterborne basecoat composition is optional.
  • Forced drying requires utilizing equipment such as blowers and/or heaters to remove solvent at a faster rate than would occur under ambient conditions, or with ambient (unforced) air flow such as, for example, the normal airflow resulting from the movement of a substrate through space on a paint process line. It can be desirable in the practice of the present invention to eliminate process steps that are not required, and thereby improve efficiency and reduce costs associated with such steps. If no forced drying step or flash step is practiced it is expected that the solvent content of the first waterborne basecoat would not be reduced substantially - that is, not greater than 5 wt% loss of solvent, compared with the weight of the applied first waterborne basecoat -- prior to applying the second waterborne basecoat.
  • Application of the second waterborne basecoat composition can be done at essentially the same temperature, humidity, and airflow conditions as used to apply the first waterborne basecoat composition.
  • the process of the present invention includes a third step 26 of subjecting the combined waterborne basecoat layers to a forced drying or flash step to volatilize at least a portion of the volatile materials from the liquid coating compositions and set, but not initiate curing or crosslinking of, the basecoats on the substrate.
  • set it is meant that the applied basecoat is dried sufficiently that it is not disturbed or marred (waved or rippled) by air currents that may blow past the surface.
  • the flash step can be conducted in heated and/or dehydrated air, such as, for example, using infra-red radiation and convection drying. If the air is heated, it can be heated to a temperature in the range of from about 60°C to 80°C.
  • the volatilization or evaporation of volatiles from the basecoat can be carried out in open air, but is preferably carried out in a flash chamber ( FIG. 1 ) in which heated and/or dehydrated air is circulated at low velocity to minimize airborne particle contamination.
  • a typical flash chamber has blowers or fans positioned at the top and sides of the chamber so that the circulated air is directed in a manner that is substantially perpendicular to the surface of the substrate.
  • the automobile body can be moved through the flash chamber in an assembly-line manner at a rate that permits the volatilization of the applied basecoat compositions as discussed above.
  • the rate at which the automobile body is moved through the flash chamber depends in part upon the length and configuration of the flash chamber.
  • An intermediate flash step can take from 30 seconds to 10 minutes. Preferably this step can take from about 2-5 minutes, as in a conventional painting process.
  • the body is dried sufficiently to enable application of the clearcoat composition such that the quality of the finish will not be affected adversely by further drying and/or curing of the basecoat.
  • the basecoats after application to the surface of the substrate, and having been subjected to the flash step, form a multilayer film that is substantially uncrosslinked.
  • the applied basecoat compositions must be sufficiently dried so that remaining water vapor does not evolve to create defects in the layers of basecoat or clearcoat composition during the baking and curing of the applied layers.
  • the process of the present invention comprises a next step 28 of applying a liquid (solventborne or waterborne) or powder clear clearcoat composition over the applied basecoat layers.
  • the clearcoat can be applied by any of the method known to those of ordinary skill in the art.
  • a liquid clearcoat can be applied over a basecoat by means of a wet-on-wet application, i.e., the clearcoat can be applied to the basecoat without curing or completely drying the basecoat.
  • the clearcoat is preferably applied over partially layers of basecoat composition that have been flashed, that is, partially dried. For the purposes of the present invention, this is referred to herein as a "wet-on-wet" process because the basecoat is not completely dried or cured.
  • the applied basecoat compositions can be cured, if desired, before the clearcoat is applied.
  • the first and second waterborne basecoat compositions and the clearcoat compositions described above can be applied by conventional techniques such as spraying, electrostatic spraying, high rotational electrostatic bells, and the like.
  • the preferred techniques for applying all three coatings are air atomized (pneumatic) spraying with or without electrostatic enhancement, and high-speed rotational electrostatic bells, since these techniques are typically employed in a continuous paint application process.
  • the process of the present invention preferably comprises a curing (i.e., baking) step 30 in which the coated substrate is heated for a predetermined time period to allow simultaneous curing of the basecoats and clearcoat.
  • the composite coating composition is baked preferably at 60-150°C for about 15-45 minutes to form a cured finish on the substrate.
  • cured means that the crosslinkable components of the coatings are substantially crosslinked.
  • substantially crosslinked it is meant that most of the crosslinking has occurred, although further crosslinking may occur over time.
  • the process of the invention can optionally include a cooling step (not shown) after the curing step to cool the composite finish to ambient temperatures before the vehicle is further worked on during its manufacture.
  • the first waterborne basecoat functions to fill in defects, such as the sanding defects present in the primer surfacer layer, and provide a smooth finish over which a second waterborne basecoat layer containing an effective amount of thin metal flakes can be applied.
  • the first basecoat is either a non-transparent solid color (pigmented) basecoat or an unpigmented basecoat.
  • non-transparent means that the contrast between the black and white fields of a black and white chart coated with the coating composition is no longer visually discernible.
  • ISO 6504-3:2006 (E) methods B is used to determine the dry film thickness of a coating composition that is applied in a wedge shape to a black and white chart at the point of complete hiding.
  • the first waterborne basecoat composition employed in the present invention is a waterborne basecoat composition, preferably a solid color pigmented or an unpigmented waterborne basecoat composition, more preferably a solid color black waterborne basecoat, that is opaque and is applied at complete hiding.
  • a waterborne basecoat composition preferably a solid color pigmented or an unpigmented waterborne basecoat composition, more preferably a solid color black waterborne basecoat, that is opaque and is applied at complete hiding.
  • Other non-transparent colored compositions can also be used, although black-pigmented compositions are preferred.
  • the first waterborne basecoat composition is preferably a crosslinkable composition comprising a film-forming binder, volatile material, and optionally pigment.
  • the film-forming binder must contain at least one water-compatible aqueous microgel, at least one crosslinking agent such as an amino resin and a sheet silicate.
  • the film-forming binder also preferably contains at least one other polyol polymer.
  • the aqueous microgels suitable for use in this invention may be composed of various types of crosslinked polymers. Of particular interest for the purposes of this invention are crosslinked acrylic microgel particles. Preparation of such acrylic microgels may be carried out by methods that are well known and routinely practiced by those of ordinary skill in the art.
  • the microgels are acrylic addition polymers mainly derived from one or more alkyl acrylates or methacrylates, optionally together with other ethylenically unsaturated copolymerizable monomers like styrene and vinyl esters.
  • Suitable alkyl acrylates or methacrylates include, without limitation, alkyl acrylates and methacrylates each having 1-18 carbon atoms in the alkyl group.
  • microgel is required to be formed with internal crosslinking, there may be included in the monomers from which the microgel is derived a minor proportion of a monomer which is polyfunctional with respect to the polymerization reaction, such as ethylene glycol dimethacrylate, allyl methacrylate or divinylbenzene.
  • the monomers may be included in the monomers minor proportions of two other monomers carrying pairs of functional groups which can be caused to react with one another either during or after polymerization, such as epoxy and carboxyl (as for example, in glycidyl methacrylate and methacrylic acid), anhydride and hydroxyl, or isocyanate and hydroxyl.
  • functional groups such as epoxy and carboxyl (as for example, in glycidyl methacrylate and methacrylic acid), anhydride and hydroxyl, or isocyanate and hydroxyl.
  • Acid functional monomers such as acrylic acid or methacrylic acid are also preferably included in the monomer mix to ionically stabilize the microgels in the aqueous dispersion medium by converting such groups to a suitable salt by reaction with a base, such as dimethylaminoethanol, dissolved in the aqueous medium.
  • a base such as dimethylaminoethanol
  • the required stability in the aqueous medium can be achieved by using an acrylate or methacrylate monomer containing basic groups, for example, N,N-dimethylaminoethyl methacrylate which is neutralized with a suitable acid, such as lactis acid.
  • Stability in aqueous medium can also be achieved through the use of surfactants or macromonomers that contain water-soluble nonionic stabilizers such as materials that contain polyethylene glycol structures.
  • the microgel preferably contains appropriate functional groups, such as hydroxy groups, whereby they can become crosslinked, after application of the composition to the substrate by means of a crosslinking agent, e.g., the amino resin.
  • aqueous carrier it is meant either water alone or water mixed with a water-miscible organic co-solvent such as an alcohol.
  • aqueous carrier it is meant either water alone or water mixed with a water-miscible organic co-solvent such as an alcohol.
  • the crosslinked microgel particles so produced are provided in colloidal dimensions.
  • the microgel particles that are particularly useful in this invention generally have a colloidal size from about 80 to 400 nanometers, in diameter, preferably from about 90 to 200 nanometers.
  • the first and second waterborne basecoat compositions can each individually include other film-forming polymers, such as polyols.
  • Suitable polyols useful for preparing the waterborne basecoat composition include water-compatible acrylic, polyester, polyurethane, polyether, or other polyol having a hydroxyl number of 50-200, as are conventional in the art.
  • Additional water-compatible film-forming and/or crosslinking polymers may be included in the basecoat employed in the present invention. Examples include water-compatible acrylics, polyurethane, epoxies, or mixtures thereof.
  • film-forming filler materials such as oligomeric polyether glycols of low volatility, for example, low molecular weight polypropylene and/or polyethylene glycol, can be used to fill the voids formed by the microgel particles upon drying and to improve the physical properties of the resulting film or finish.
  • oligomeric substances can be converted to high molecular weight polymer, after application of the basecoat composition, by linking them through their hydroxyl groups or other groups that are reactive with the crosslinking agent.
  • Suitable crosslinking agents include aminoplast resins that are soluble or partially soluble in the aqueous medium of the composition, such as melamine-formaldehyde condensates and in particular alkylated (e.g., methylated, butylated) melamine-formaldehyde condensates.
  • Other contemplated crosslinking agents are alkylated urea formaldehyde condensates, benzoguanamine formaldehyde condensates and blocked polyisocyanates or compatible mixtures of any of the forgoing.
  • a useful first waterborne basecoat composition comprises aqueous microgel in an amount of from about 20-70% by weight of binder solids, preferably 45-65% by weight, in addition to coloring pigments.
  • Suitable aqueous microgels include but are not limited to the crosslinked acrylic microparticle aqueous dispersions disclosed in U.S.
  • Patent 4,403,003 water-soluble or partially water-soluble aminoplast resin, preferably a methylated melamine formaldehyde, from 10-35%, preferably 15-25%; water dispersible polyester polyol resin from about 0-30%; polyurethane polyol aqueous dispersion from 0-35%, preferably 5-15%; water soluble polyether filler from 0-15%; water-soluble acid catalyst from about 0-2%, such as but not limited to a volatile amine blocked sulfonic acid catalyst, to promote melamine or other crosslinking reaction.
  • water-soluble or partially water-soluble aminoplast resin preferably a methylated melamine formaldehyde, from 10-35%, preferably 15-25%
  • water dispersible polyester polyol resin from about 0-30%
  • polyurethane polyol aqueous dispersion from 0-35%, preferably 5-15%
  • water soluble polyether filler from 0-15%
  • water-soluble acid catalyst from about 0-2%, such
  • the first waterborne basecoat composition also includes 0.1-1.6%, preferably 0.2-1%, based on the weight of the total composition, sheet silicate particle, such as those disclosed in Berg et al. U.S. Patent 5,198,490 issued Mar. 30, 1993 , to help give the desired holdout or resistance to strike-in and intermixing.
  • the overall solids content of the first waterborne basecoat composition can range from about 10 to 50% by weight of the total composition. Preferably, the overall solids content of the first waterborne basecoat can range from about 20 to 40% by weight of the total composition.
  • the first waterborne-basecoat composition is a "straight-shade" or “solid color” coating that has no visible flop or two tone metallic effect and primarily contains colored pigments other than flake.
  • Colored pigments useful in the practice of the present invention include, for example, metal oxides such as titanium dioxide, zinc oxide, iron oxides of various colors; carbon black; filler pigments such as talc, china clay, barytes, carbonates, silicates; and organic colored pigments such as quinacridones, phthalocyanines, perylenes, azo pigments, indanthrone blues, carbazoles such as carbazole violet, isoindolinones, isoindolones, thioindigo reds, benzimidazolinones, diketo-pyrrolo-pyrroles (DPP).
  • metal oxides such as titanium dioxide, zinc oxide, iron oxides of various colors
  • carbon black such as talc, china clay, barytes, carbonates, silicates
  • organic colored pigments such as quinacridones, phthalocyanines, perylenes, azo pigments, indanthrone blues, carbazoles such as carbazole violet, iso
  • effect pigments such as aluminum flakes, copper bronze flakes, pearlescent flakes, and the like, and optional other effect pigments, holographic flakes, glass spheres, glass flakes, other non-flake effect pigments including micro titanium dioxide pigments and GRAPHITAN ® pigments, and higher degree effect pigments including, for instance, CHROMAFLAIR ® , VARIOCHROME ® , and HELICONE ® pigments, can be optionally included in the first waterborne basecoat composition to impart the desired color effect and hiding.
  • the metal flake pigments optionally used in the first waterborne basecoat are distinguished from the thin metal flake pigments of the second waterborne basecoat composition.
  • Metal flakes of the first basecoat have an average particle thickness in the range of from 300 to 500 nanometers and average particle diameters in the range of from 5 to 60 micrometers. They are significantly thicker than the thin metal flake pigments of the second waterborne coating.
  • Typical inhibitors are phosphated organic materials such as phosphoric acid and other materials as described in U.S. Pat. No. 4,675,358 .
  • the specifc pigment to binder ratio of the first waterborne basecoat can vary widely so long as it provides the requisite hiding at the desired film thickness and application solids.
  • the pigments can be introduced into either the first or second waterborne basecoat compositions by forming a mill base or pigment dispersion with any of the aforementioned polymers used in the coating compositions or with another compatible polymer or dispersant by conventional techniques, such as high speed mixing, media milling, sand grinding, ball milling, attritor grinding or two/three roll milling. It is known conventionally that milling techniques are not applicable for metal flake pigments. It is therefore conventional that mixing and slurry techniques are used to disperse flake pigments.
  • the pigment dispersion can be blended with the other constituents used in the coating compositions.
  • the first and second waterborne basecoat compositions are formulated to have acceptable hold-out or resistance to intermixing between the basecoats within about 10 to 300 seconds after application at ambient conditions between coats, preferably within 1 to 4 minutes under ambient conditions.
  • Ambient conditions mean the environmental conditions in a typical painting facility. Typical ambient conditions are: a temperature in the range of from 15°C to about 35°C; a relative humidity in the range of from 5 percent to 90 percent; and, for a continuous paint line, a line speed in the range of from about 2 meters/minute to about 11 meters/minute.
  • the coating materials described herein are formulated so that they can be applied in conditions ranging from 18°C to 28°C and a relative humidity of 50 percent to 70 percent.
  • An additional step of flashing a portion of the aqueous carrier from the first waterborne basecoat layer before applying the second waterborne basecoat composition is not required nor is such a step desirable.
  • a continuous painting facility that is, a painting facility utilizing a continuously moving paint line using a "wet on wet" process
  • no substantial evaporation of the solvent from the first waterborne basecoat occurs during the time between the completion of the first waterborne basecoat and the start of the application of the second waterborne basecoat.
  • the second waterborne basecoat composition can be applied over the first layer under the same or similar spraybooth conditions as used when applying the first waterborne basecoats without sacrificing good control of the orientation of the thin metal flake pigments, and without detracting from the desirable appearance (i.e. a minimum of perceptible sparkle, high brightness, large flop value, polished or anodized metal appearance) of the overall finish.
  • the first waterborne basecoat can be applied at such a rate as to achieve a dry film thickness in the range of from 5 to 40 microns, preferably in the range of from 15 to 30 microns.
  • the second waterborne basecoat can be applied so as to achieve a dry film thickness in the range of from 2 to 10 microns, preferably in the range of from 2 to 4 microns.
  • the solids content of the second waterborne basecoat can be kept low relative to that of the solids content of the first waterborne basecoat.
  • the solids content of the second waterborne basecoat can be in the range of from about 3% to about 30% by weight of the total composition.
  • the solids content of the second waterborne basecoat can be in the range of from 5% to 15%, by weight of the total composition.
  • the second waterborne basecoat composition employed in this invention provides the polished metal effect and is a differently pigmented composition that its formulated to be, like the first waterborne basecoat composition, non-transparent (opaque) and is applied at complete hiding.
  • the second waterborne basecoat composition comprises an effective amount of thin metal flake pigment to impart the desired polished metal effect.
  • An effective amount of thin metal flake pigment for the purposes of the present invention, is the amount of thin metal flake contained in a binder composition in a thin metal flake to binder ratio of from 1/100 up to 100/100 preferably from 3/100 up to 50/100, and most preferably from 10/100 up to 40/100.
  • thin metal flake pigment means a metal particle having an average particle thickness in the range of from about 10 to 100 nanometers and an average particle diameter in the range of from about 5 to 30 micrometers.
  • the thin metal flake pigments Preferably, have an average thickness in the range of from about 15 to 40 nanometers and an average particle diameter in the range of from about 8 to 20 micrometers.
  • Such thin metal flake pigments have an aspect ratio (the ratio of the flake diameter to the flake thickness) that is very high (in the hundreds rather than traditional flake pigments in the tens).
  • These thin metal flake pigments can be produced by coating a very thin layer of metal vapor onto pretreated polyester film in a vacuum chamber and then solvent stripping the deposited metal layer from the carrier film.
  • the thin metal flake pigments may be unpassivated or passivated. Passivated types are, for example, phosphated, chromated or coated with a silicon-oxygen network. Passivated types are preferably used.
  • Such thin metal flake pigments are commercially available in passivated and unpassivated forms as pigment preparations under the names HYDROSHINE ® and METALURE ® , both available from Altana/Eckart, Hundth, Germany; METASHEEN ® available from Ciba, Basel, Switzerland; DECOMET ® available from Schlenk, Roth, Germany and STARBRITE ® , available from Silberline, Tamaqua, Pennsylvania.
  • the second waterborne basecoat composition may optionally also contain one or more other traditional flake pigments such as standard aluminum flake pigments and/or flake pigments. It may also optionally contain other colored pigments to give the desired color effect, such as any of those listed above.
  • the second waterborne basecoat is a silver color basecoat.
  • Preferred second waterborne basecoat compositions contain film forming binders that are similar to the first basecoat composition and include an aqueous microgel, such as but not limited to the crosslinked aqueous microgel dispersions disclosed in aforementioned U.S. Patent 4,403,003 , optional polyol polymer, a crosslinking agent, such as an amino resin, an effective amount of thin metal flake pigment and sheet silicate. Any of the microgels, polyols, and crosslinking resins described as useful in the first basecoat can be used in the second waterborne basecoat composition.
  • One useful second waterborne basecoat composition in addition to the thin metal flake pigments and optionally other pigments, comprises by weight of binder solids, aqueous microgel from about 20-70%, preferably 45-65%, water-soluble or partially water-soluble aminoplast resin, preferably a methylated melamine formaldehyde, from about 10-35%, preferably 1-5-25%, water dispersible polyester polyol resin, from about 0-30%, polyurethane polyol aqueous dispersion from about 0-35%, preferably 15-25%, water-soluble polyether filler from 0-10%, blocked acid catalyst from about 0-2%, such as but not limited to amine blocked sulfonic acid catalyst, to promote melamine or other crosslinking reaction.
  • the composition also includes 0.1-1.6%, preferably 0.3-1%, based on the weight of the total composition, sheet silicate particle to help give the desired holdout or resistance to strike-in and intermixing.
  • the second waterborne basecoat composition can optionally include other pigments such as color providing pigments or other flake effect pigments.
  • the pigments can be introduced into the second waterborne basecoat composition by first forming a mill base or pigment dispersion with any of the aforementioned polymers used in the coating composition or with another compatible polymer or dispersant by conventional techniques, such as mixing/slurrying (i.e., for flakes), high speed mixing, media milling, sand grinding, ball milling, attritor grinding or two/three roll milling. Milling techniques may not be applicable for metal flake pigments. Mixing and slurry techniques can be used to disperse flake pigments. The pigment dispersion can be blended with the other constituents used in the coating composition.
  • Both first and second waterborne basecoat compositions employed in the present invention may also include other conventional formulation additives such as wetting aids, surfactants, defoamers, UV fortifiers, and rheology control agents, such as fumed silica, alkali swellable emulsions, associative thickeners, or water compatible cellulosics.
  • Both first and second waterborne basecoat compositions employed in this invention also include volatile materials such as water alone or water and a mixture of conventional organic solvents and diluents, to disperse and/or dilute the above mentioned polymers and facilitate formulation and spray application.
  • Typical organic co-solvents and diluents include hexyl CELLOSOLVE ® , toluene, xylene, butyl acetate, acetone, methyl isobutyl ketone, methyl ethyl ketone, methanol, isopropanol, butanol, butoxyethanol, hexane, acetone, ethylene glycol, monoethyl ether, VM and P naptha, mineral spirits, heptane and other aliphatic, cycloaliphatic, aromatic hydrocarbons, esters, ethers and ketones and the like.
  • water is used as the major diluent.
  • Amines such as alkanolamine can also be used as a diluent.
  • both the first and second waterborne basecoats include the required amounts of both aqueous microgel and sheet silicate.
  • the combination of the two in each' of the basecoat compositions functions to provide coating compositions that once applied to a substrate, have the required resistance to intermixing. This allows the first waterborne basecoat to provide a flat and smooth surface on which to apply the second waterborne basecoat containing the thin metal flake pigments and prevent intermixing of the two layers that would destroy the desired polished metal effect.
  • the nature of the clearcoat composition employed in the process of the present invention is not critical. Any of a wide variety of commercially available automotive clearcoat compositions may be employed in the present invention including standard solventborne, waterborne, or powdered clears. High solids solventborne clearcoats that have low VOC (volatile organic content) and meet current pollution regulations are generally preferred. Typically useful solventborne clearcoats include but are not limited to 2K (two-component) systems of polyol polymers crosslinked with isocyanate and 1 K systems of acrylic polyol crosslinked with melamine or 1 K acrylosilane systems in combination with polyol and melamine. Epoxy-acid systems can also be used.
  • Suitable 1 K solventborne acrylosilane clearcoat systems that can be used in the process of the present invention are known and disclosed in U.S. Patent 5,162,426 .
  • Suitable 1 K solventborne acrylic/melamine clearcoat systems are disclosed in U.S. Patent 4,591,533 .
  • the above described multilayer coating composition can be used to provide automobiles and trucks with a polished metal-like or anodized metal-like exterior finish having an attractive aesthetic appearance, including high gloss and DOI (distinctness of image), even on prolonged exposure to the environment and weathering. Matte finish clearcoats can provide the same effect, without the high gloss and DOI traits of a gloss clearcoat.
  • Useful substrates that can be coated according to the process of the present invention include a variety of metallic and non-metallic substrates such as plastic substrates, and combinations thereof.
  • Useful metallic substrates that can be coated according to the process of the present invention include unprimed substrates or previously painted substrates, cold rolled steel, phosphatized steel and steel coated with conventional primers by electrodeposition.
  • Useful plastic materials include polyester reinforced fiberglass, reaction-injection molded urethanes, partially crystalline polyamides, and the like or mixtures thereof and their associated primers.
  • the substrates are used as components to fabricate automotive vehicles, including but not limited to automobiles, trucks, and tractors.
  • the substrates can have any shape, but are usually in the form of automotive body components such as bodies, hoods, doors, fenders, bumpers and/or trim for automotive vehicles.
  • the invention is most useful in the context of coating automotive bodies and components thereof traveling in continuous movement along an automotive assembly line.
  • the following pigment slurry was prepared with 35.5 grams (g) of de-ionized water, 10.0g of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 20.0g butoxyethanol, 15.0g CYMEL ® 303, 5.0g SOLSPERSE ® 20000 and 7.0g of 10% aqueous dimethylethanol amine solution and 0.5g SURFYNOL ® 104.
  • the above components were mixed together, 7.0g of CARBON BLACK FW 200 ® pigment was added and the resulting slurry was pre-dispersed using a Cowles blade. The mixture was then ground in a horizontal beadmill until the desired particle size of less than 0.5 micron was achieved.
  • the following pigment slurry was prepared with 46.3g of de-ionized water, 15.0g of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 20.0g butoxyethanol, 8.0g CYMEL ® 303, 2.0g SOLSPERSE ® 20000, 0.2g of 10% aqueous dimethylethanol amine solution and 0.5g SURFYNOL ® 104.
  • the above components were mixed together and 8.0g of PALIOGEN ® Red L 3885 pigment was added and the resulting slurry was pre-dispersed using a Cowles blade. The mixture was then ground in a horizontal beadmill until the desired particle size of less than 0.5 micron was achieved.
  • a homogeneous blend was prepared by mixing together and stirring 47.5g of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 2.0g of butoxyethanol and 0.5g of SURFYNOL ® 104. Following this, 50.0g of 3% LAPONITE ® RD in de-ionized water was added under stirring and homogenized and dispersed using a horizontal beadmill.
  • a first waterborne black basecoat composition was prepared by mixing together the following constituents under constant agitation in the order stated: 26.8 pbw of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 16.2 pbw of black pigment dispersion, 5.8 pbw of CYMEL ® 303, 13.8 pbw of rheology base, 1.0 pbw of SURFYNOL ® 104, and 2.0 pbw of butoxyethanol.
  • This example shows the preparation of a first waterborne basecoat composition without the addition of sheet silicate.
  • a waterborne black basecoat composition was prepared by mixing together the following constituents under constant agitation in the order stated: 36.0 pbw of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 16:2 pbw of black pigment dispersion, 5.8 pbw of CYMEL ® 303, 1.0 pbw of SURFYNOL ® 104, and 2.0 pbw of butoxyethanol.
  • This example shows the preparation of a basecoat composition without the addition of the aqueous acrylic microgel.
  • the preparation of the first waterborne black basecoat composition was repeated with the difference that the entire portion of the 30% non-volatile hydroxy functional aqueous acrylic microgel (including any aqueous acrylic microgel contained in the premixes used) was replaced by an aqueous polyurethane dispersion DAOTAN ® VTW 1236. This replacement was performed according to an 1:1 replacement of binder solids.
  • a waterborne silver color basecoating composition was prepared by mixing together the following constituents under constant agitation in the order stated: 13.0 pbw of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 12.4 pbw of HYDROSHINE ® WS-3001, 3.4 pbw of CYMEL ® 303, 4.2 pbw of Rheology base, 1.0 pbw of butoxyethanol, and 1.0 pbw of SURFYNOL ® 104.
  • This examples shows the preparation of a basecoat composition without the addition of sheet silicate.
  • a waterborne silver color basecoating composition was prepared by mixing together the following constituents under constant agitation in the order stated: 15.9 pbw of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 11.7 pbw of HYDROSHINE ® WS-3001, 3.4 pbw of CYMEL ® 303, 1.0 pbw of butoxyethanol, and 1.0 pbw of SURFYNOL ® 104.
  • This example shows the preparation of a basecoat composition without the addition of the aqueous acrylic microgel.
  • the preparation of the second waterborne silver basecoat composition was repeated with the difference that the entire portion of the 30% non-volatile hydroxy functional aqueous acrylic microgel (including any aqueous acrylic microgel contained in the premixes used) was replaced by an aqueous polyurethane dispersion DAOTAN ® VTW 1236. This replacement was performed according to an 1:1 replacement of binder solids.
  • a waterborne silver-red color shade basecoating composition was prepared by mixing together the following constituents under constant agitation in the order stated: 10.3 pbw of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 7.5 pbw of HYDROSHINE ® WS-3001, 2.5 pbw of CYMEL ® 303, 9.3 pbw of red pigment dispersion, 4.0 pbw of rheology base, 1.0 pbw of butoxyethanol and 1.0 pbw.
  • SURFYNOL ® 104 10.3 pbw of a 30% non-volatile hydroxy functional aqueous acrylic microgel, 7.5 pbw of HYDROSHINE ® WS-3001, 2.5 pbw of CYMEL ® 303, 9.3 pbw of red pigment dispersion, 4.0 pbw of rheology base, 1.0 pbw of butoxyethanol and 1.0 pbw.
  • the clearcoat composition used for the examples was a collision baking clear, commercially available from Du Pont Performance Coatings (Standox), Christbusch 25, D-42285 Wuppertal, Germany, prepared by mixing STANDOCRYL ® 2K-HS Clearcoat, 020-82497, with STANDOX ® 2K-HS Hardener, 020-82403, in a 2:1 volume ratio.
  • Standard automotive metal substrates (car doors) were processed and prepared with standard automotive pre-treatment, and dried and cured layers of electrocoat and primer. The substrates were then processed through a standard continuous basecoat/clearcoat automotive type application line at a continuous line speed of approximately 4 m/min, according to Table 1.
  • the first waterborne black basecoat composition and comparative first waterborne black basecoat compositions A and B were applied with an electrostatic bell at a flow rate of 120. cc/min.
  • the second waterborne silver basecoat composition, comparative second waterborne silver basecoat composition A, comparative second waterborne silver basecoat composition B and second waterborne silver-red basecoat composition were applied over the applied first waterborne basecoats according to Table 1.
  • Each of the second waterborne basecoat compositions were applied on top of the first waterborne black basecoat compositions wet on wet, by pneumatic atomization with robots, at a flow rate of 500 cc/min. The applied coatings were then dried by a standard force dry in a drying tunnel for approximately 5 minutes at 60°C. Following the drying step, the solventborne clearcoat composition was applied using electrostatic spray gun, and the substrate was baked 10 minutes at 120°C.
  • the film builds were as follows: First waterborne basecoat: 15 - 18 microns Second waterborne basecoat: 2 - 4 microns Clearcoat: 40 - 45 microns
  • the multilayer coated car doors were in each case visually rated by 5 independent individuals according to the following scale; 1 - Good polished metal effect; i.e., a highly reflective coating with a polished or anodized metal effect was obtained. No occurrence of intermixing or strike-in phenomena. 2 - No polished metal effect. The system exhibited some intermixing and strike-in. Some sparkling. 3 - No polished metal effect. The system exhibited strong intermixing and strike-in. Greyish appearance.
  • Second waterborne silver-red basecoat composition 1 n/t n/t n/t means that the particular combination of basecoat compositions was not sprayed.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (8)

  1. Processus d'application de multiples couches de revêtement sur un substrat pour obtenir une apparence métallique brillante, le processus comprenant les étapes consistant à :
    (a) appliquer sur au moins une surface du substrat une composition de couche de fond à base d'eau de couleur noire solide qui est essentiellement exempte de fins pigments de flocons métalliques pour obtenir un substrat revêtu ;
    (b) appliquer sur le substrat revêtu de l'étape (a) une composition de fond à base d'eau pigmentée comprenant une quantité efficace de fins pigments de flocons métalliques pour transmettre l'effet métallique brillant souhaité, ledit pigment à flocons métalliques fins possédant une épaisseur moyenne dans la gamme comprise entre 10 et 100 nanomètres et possédant un diamètre de particules moyen dans la gamme comprise entre 5 et 30 micromètres ;
    (c) soumettre le substrat revêtu obtenu dans l'étape (b) à une étape de séchage éclair ;
    (d) appliquer une composition de revêtement transparent sur le substrat revêtu obtenu dans l'étape (c) ; et
    (e) sécher les revêtements appliqués lors des étapes (a), (b), et (d) simultanément dans une cuisson unique pour obtenir un substrat revêtu possédant une apparence métallique brillante ;
    dans lequel les première et seconde compositions de couche de fond à base d'eau comprennent un microgel aqueux et les première et seconde compositions de couche de fond à base d'eau contiennent un phyllosilicate,
    dans lequel la première composition de couche de fond à base d'eau est opaque et est appliquée avec masquage total, et
    dans lequel la seconde composition de couche de fond à base d'eau est formulée pour être non transparente et est appliquée avec masquage total.
  2. Processus selon la revendication 1, dans lequel les première et seconde compositions de couche de fond à base d'eau contiennent dans la gamme allant de 20 pourcent à 70 pourcent en poids, sur la base du poids du liant filmogène, d'un microgel aqueux.
  3. Processus selon la revendication 1 ou 2, dans lequel les première et seconde compositions de couche de fond à base d'eau contiennent dans la gamme allant de 0,1 pourcent à 1,6 pourcent en poids, sur la base du poids de la composition de couche de fond, de phyllosilicate.
  4. Processus selon la revendication 3, dans lequel la teneur en solide de la seconde couche de fond à base d'eau est inférieure à la teneur en solide de la première couche de fond à base d'eau.
  5. Processus selon la revendication 4, dans lequel la première composition de couche de fond à base d'eau est appliquée en utilisant un équipement de pulvérisation électrostatique ou pneumatique.
  6. Processus selon la revendication 5, dans lequel la seconde composition de couche de fond à base d'eau est appliquée en utilisant un équipement de pulvérisation électrostatique ou pneumatique.
  7. Processus selon la revendication 6, dans lequel le processus se passe sur une chaîne d'assemblage déplaçant de manière continue.
  8. Processus selon la revendication 7, dans lequel la chaîne d'assemblage se déplaçant de manière continue est une chaîne d'assemblage pour automobiles.
EP08858291.1A 2007-11-28 2008-11-24 Procédé de production d'un fini à effet métallique poli sur un véhicule Active EP2212031B1 (fr)

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US27559208A 2008-11-21 2008-11-21
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DE112012004576B4 (de) * 2011-11-01 2022-05-05 Coatings Foreign Ip Co. Llc Verfahren zur Vorhersage metallischen Glanzes einer Beschichtung resultierend von Beschichtungszusammensetzungen durch Nassfarbmessungen
JP7213085B2 (ja) 2018-12-25 2023-01-26 日本ペイント・オートモーティブコーティングス株式会社 複層塗膜形成方法

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US20040028822A1 (en) * 2002-08-08 2004-02-12 Wilfried Dutt Continuous process for applying a tricoat finish on a vehicle
US20060008588A1 (en) * 2004-07-12 2006-01-12 Marc Chilla Process for the production of multi-layer coatings
US20070071901A1 (en) * 2005-09-29 2007-03-29 Giannoula Avgenaki Process for the production of multi-layer coatings

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